Processes of separating nitrile-hydrocarbon mixtures by means of amines



' 'umrao STAT .5 erential solvent material can be crack I controlled that enable themto be 1' have been so Patented Jan. 31, 1939 1 PROCESSES F DBOCARBON AMINES ES PATENT OFFICE sarana'rmo NrrmLE-nx- MIXTURES BY MEANS or Anderson W. Ralston and William 0. Pool, Chi- Q l i m,

, assignors to Armour and Company,

. Chica go, Ill.,'a corporation of Illinois No Drawing." Original application July 9, 1936,

Serial No. 89,850. Divided and this application October 15, 1937, Serial No.

8 Claims. (01. 260-464) This invention relates to processes of sepa- 1 rating aliphatic nitriles from admixtures thereof with hydrocarbons and-it comprises processes wherein such mixtures areftreated with a preffor the nitriles to form an extract phase containing the nitrile dissolved "in the solvent and a hydrocarbon phase, the two phases separated and the nitrile then separated from the extract phase.

Recently processes have been described, as in q .11. 8. Patents 1,991,955, 2,033,536 and 2,033,537, for preparing nitriles of relatively low molecular weight from nitriles of high molecular weight.

For example, by methods of pyrolysis higher aliil phaticnitriles such as stearo and palmitonitrile "to give reaction products containing nitriles having four, flve, six and seven carbon atoms. The cracking operation can be nitriles of almost any desired Q numberof carbon atoms say-from six to eleven can be prepared from nitriles of higher molecular weight. In these processes the reaction products are homogeneous liquid mixtures containing various'nitriles associated with quantities of all- 8| phatic hydrocarbons.

- 7 Although the cracked reaction mixtures have many uses as such without further treatment, there are many instances when it is desirable to separate the nitriles from the hydrocarbons and I to then fractionally .distil the separated nitriles. This will yieldsubstantially pure'nitriles. And

' i e the pure nitrilesare starting materials for many pounds of this nature have not been available on and at a price which would. used in great quantities. In

a commercial scale other words, the development of prooesses'of pre- 0 paring nitriles from the cheap fatty acid sources has made it possible for us'to supply large quantities of aliphatic compounds having from about five to ten carbon atoms ,in the alkyl group, together with a highly reactive 'polar, or CN group.

i I I This means that many'aliphatlc amines,'alcohols and acids, of fromlsix to ten carbon atoms can be prepared at low cost. Hitherto these materials nitriles'and hydrocarbons in thismanner. Constant boiling mixtures are obtained in many inbe fractionally expensive that they could not be stances and there are other objections. The most productive source of the lower nitriles is the higher fatty acid nitriles because of the ease with which these can be cracked to give the desired lower nitrlles. But, as stated, the cracked products contain quantities of hydrocarbons.

Consequently, we have set ourselves to the problem of discovering methods by which these mixtures of nitriles and hydrocarbons can be separated to obtain the nitriles which can then distilled if desired. And we have discovered that mixtures of this type can be treated with preferential solvents in such a manner that the nitriles are dissolved to the exclusion of the hydrocarbons. From the extract phase of nitriles and solvent we can thenrecover the nitriles and recover the solvent for re-use. Many experiments have been necessary, however, since what will or will not act as a preferential solvent for such mixtures could not be determined in advance of experiment. Many solvents which might seemingly dissolve the nitriles without affectin the hydrocarbons actually form homogeneous mixtures without leading to the formation of stratified layers of hydrocarbon and nitrile extract. Because of the pronounced mutual solubility of the nitriles and aliphatic hydrocarbons,

many solvents dissolve the nitrile but the nitrile acts as a mutual second solvent for both hydrocarbon and added solvent. This leads to mutual solution of all constituents. Consequently, the search for satisfactory preferential solvents has 'been a difficult task and many unexpected discoveries have been made.

For example, we have discovered that watery solutions of aliphatic alcohols can be used successfully provided care is taken to control the quantity of water present.- Thus a 75 percent solution-of methyl alcohol will dissolve the nitrile but not the aliphatic hydrocarbons present but 85 percent methyl alcohol forms a homogeneous solution of alcohol, water, nitriles, and hydrocarbons. Hence the application of the broad, old idea of preferential extraction with a suitable solvent to mixtures of the type with which we are concerned has not been a simple matter.

Moreover, having discovered a suitable preferential solvent which will give an extract containing nitriles dissolved in the solvent, the next step is the liberation of the dissolved nitrile from the extract. Here again many solvents, ap-

parently suitable as preferential solvents must be discarded because of the difliculties in separating the nitrile therefrom. What we have sought is compounds which can be clean stratification into two liquid layers, and which, by the addition or something to the extract layer, would then liberate the nitrile. These requirements have made the search for solvents prolonged.

We have, however, discovered four classes oi. used in our process and, since we are the first to deal with this problem, and to describe its solution, tion broadly in the appended claims. We believe ourselves to be the first to propose the use of preferental solvents in this art in such a manner that the nitriles are liberated from the extract phase by the addition of substances thereto which decrease the solubility of the'preferential solvent for the nitrile in the extract.

We have discovered that aliphatic alcohols, phenolic compounds like phenol and the cresols, amino compounds generally aliphatic but including aniline, and the water soluble aliphatic carboxylic acids can be used under certain conditions as preferential solvents and that from the extract phase composed of solvent and nitriles we can separate the nitriles simply by adding something to the extract which acts to decrease the solubility of the nitriles.

We shall first describe our invention with reference to the use of the aliphatic alcohols. All of the alcohols which we use are miscible with water and among. them we can use methyl, ethyl, propyl, both normal and .iso, butyl, benzyl, furfuryl, tertiary butyl, secondary butyl, allyl, diamyl,

secondary amyl and cyclohexyl. When using the alcohols we first treat the mixture of nitriles and hydrocarbons with a watery solution of the alcohol, the amount of water present being such that the nitriles are soluble in the watery alcohol but the hydrocarbons are not. We then separate ofi the upper layer of hydrocarbons from the lower extract phase composed of nitriles dissolved in the watery alcohol. Upon theaddition of more water to the extract so as to decrease the actual concentration of alcohol the nitriles separate out since they are not soluble in extremely diluted alcohol.

As stated, the various alcohols listed above can be used but for the sake of brevity we shall describe detailed examples using methyl alcohol.

One hundred parts by volume of a nitrilehydrocarbon mixture obtained-by cracking stearonitrile is mixed with 100 parts by volume of 75 percent methyl alcohol (75 percent alcohol, 25

percent water). Stratification occurs and the upper layer of hydrocarbons is separated ofi. These hydrocarbons still contain some nitriles and are advantageously re-extracted with 100 parts of 80 percent methyl alcohol. The hydrocarbon layer isagain separated and again extracted with 100 parts by volume of 85 percent alcohol. The final hydrocarbon layer, amounting to 60 volumes, contains only 0.1 percent nitrogen. The three alcoholic lower layers, or extract I phase, from the three extractions are united and water added thereto until the nitriles therein separate as an upper layer which can be readily decanted. This upper layer amounts to 40 parts and has a nitrogen content of 8.9 percent. The methyl alcohol layer, after dilution as described, has a concentration of about 60 percent methyl alcohol. It can be recovered for reuseby distillation.

Instead of using threeextractions with increasing strengths ofalcohol we can extract directly with percent methyl alcohol and get good] results. Or the 80 percent methyl alcohol can be we claim our invenrun into the top or a column 0! the nitrilehydrocarbon mixture and the extract phase recovered continuously from the bottom of the column.

However, the strength of alcohol must be 5 alcohol of increasing strength. The more dilute alcohol removes the very low molecular weight nitriles which tend to make the hydrocarbons miscible with stronger alcohol. After the lower nitriles have been removed thenthe strength of the alcohol can be increased to percent as described. If 85 percent alcohol were used directly a homogeneous mixture showing no stratification of hydrocarbons would result.

Normal propyl alcohol can be used in the same manner and the same concentrations as methyl alcohol. When using ,the other alcohols described above preliminary experiments should be run to determine the appropriate strength of alcohol for the extraction. This can be readily done on a small scale before treating large volumes of nitrile-hydrocarbon mixture.

We shall now describe modifications of our invention using aliphatic carboxylic acids as preferential solvents. All the acids we use are miscibleat least to some extent with water. Among them can be mentioned the following. Acetic, propionic, acrylic, iso-valeric, normal valeric, isobutyric, normal butyric and caproic.

This modification is well illustrated by reference to the use of acetic. For example, we mix parts of nitrile-hydrocarbon mixture with 100 parts of glacial acetic acid containing 4 parts of water. The mixture is cooled to 0 C. at which temperature stratification occurs. The upper layer or phasefis composed of 56 parts of hydrocarbons containing 1.3 percent nitrogen. The lower layer or extract phase amounting to 144 parts contains the acetic acid and nitrile. To this lower layer we add 100 parts of water which results in the separation of an upper layer amounting to 52 parts which consists essentially of nitriles and contains 5.5 percent nitrogen. Any acetic acid present can be removed from the nitrile layer by washing with water. The hydrocarbon layer can again be extracted with the strong acetic acid to recover more nitrile therefrom. All quantities above are parts by volume.

- As stated above, phenols are also suitable solvents. Among them we can use ordinary phenol, and ortho, metal, and para cresols. For example, we mix 100 parts by volume of the cracked nitrile mixture with 100 parts by volume of phenol and 30 parts by volume of water. The. mixture is cooled to 0 C. which gives three layers. The bottom layer consists essentially of pure water, the top layer contains 36 parts of hydrocarbons in which the nitrogen content is 0.6 percent. The middle layer amounts to 168 parts by volume and contains pyenol, water, and nitriles. To this middle layer we add dilute sodium hydroxide solution, about a 10 percent solution, until the nitrile is liberated. This gives If desired the hydrocarbon 70 ammo:

mal propyl amine, diethyl amine, allyl amine, benzyl amine, secondary butyl amine, isobutyl 1 amine, normal butyl amine, isoallyl amine, normal amyl amine, dinormal propyl amine, pyridine, diallyl amine and cyclohexyl amine. For

example, 100 parts by volume of the nitrile-,- hydrocarbon mixture is mixed with 100 parts-by volume of aniline and the mixture cooled to 02 0- This gives an upper layer consisting of 40 parts of hydrocarbons containing 0.5 percent nitrogen and a lower layer composed of 160 ,parts'by volume containing aniline and nitriles"; To this lower layer we pdd dilute hydrochloric acid solualcohol solutions as preferential solvents.

Having thus described our invention, what we claim is:

1. The process of separating aliphatic nitriles I from admixture thereof with hydrocarbons which comprises treating the mixture with a preferential solvent composed of an amine liquid at temperature of from 0 C. to room temperature I and capable of dissolving the nitriles to form an extract phase containing the nitriles dissolved in said solvent and a hydrocarbon phase, separating the phases, adding a dilute water soluble,

anon-oxidizing acid capable of forming salts with the amine to the extract phase to liberate the nitriles therein as a layer and separating the nitrile layer.

2. The process of separating aliphatic nitriles from admixture thereof with hydrocarbons, said mixture resulting from the cracking of high molecular weight fattyacid nitriles, which comprises treating the mixture with a preferential solvent composed of an amine liquid at temperature of from 0 C. to room temperature and capable of dissolving the nitriles to form an extract phase containing the nitriles dissolved in said solvent and'a hydrocarbon phase, separating the phases, adding a dilute water soluble, non-oxidizing acid capable of forming salts with the shrine to the extract phase to liberate the nitriles therein as a layer and separating the nitrile layer.

3. The process as in claim 1 wherein the nitrilehydrocarbon mixture and solvent is cooled to a temperature of about 0 C. prior to separating the phases.

4. The process as in claim 2 wherein the nitrilehydrocarbon mixture and solvent is cooled to a temperature of about 0 C. prior to separating the phases. a

5. The process as in claim 1 wherein the preferenti'al solvent is aniline.

6. The process as in claim 2 wherein the preferential solvent is aniline.

7. The process as in claim 1 wherein the preferentialsolvent is an aliphatic amine.

8. The process as in claim 2 wherein the preferential solvent is an aliphatic amine.

ANDERSON W. RALSTON. WIILIAM O. POOL. 

